WO1996033243A1 - Composition de resine de revetement - Google Patents

Composition de resine de revetement Download PDF

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Publication number
WO1996033243A1
WO1996033243A1 PCT/JP1996/001036 JP9601036W WO9633243A1 WO 1996033243 A1 WO1996033243 A1 WO 1996033243A1 JP 9601036 W JP9601036 W JP 9601036W WO 9633243 A1 WO9633243 A1 WO 9633243A1
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WO
WIPO (PCT)
Prior art keywords
group
resin
component
coating
formula
Prior art date
Application number
PCT/JP1996/001036
Other languages
English (en)
Japanese (ja)
Inventor
Junko Okibe
Minoru Inoue
Motoaki Haruna
Ayumu Yasuda
Takeshi Sunaga
Yasuyo Iwabuchi
Norio Sato
Original Assignee
Matsushita Electric Works, Ltd.
Toshiba Silicone Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Works, Ltd., Toshiba Silicone Co., Ltd. filed Critical Matsushita Electric Works, Ltd.
Priority to KR1019970707487A priority Critical patent/KR100250342B1/ko
Priority to US08/750,745 priority patent/US6090873A/en
Priority to EP96909379A priority patent/EP0822240B1/fr
Priority to DE69623947T priority patent/DE69623947T2/de
Publication of WO1996033243A1 publication Critical patent/WO1996033243A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5035—Silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/65—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/70—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a coating resin composition, a resin-coated product, and a method for producing the same. More specifically, a pot plate such as stainless steel; a non-ferrous metal such as aluminum; an inorganic building material such as concrete and slate; A resin composition for coating that can be formed by coating on the surface of a base material such as wood and leaving it at room temperature or by heat treatment to form a coating film having high hardness, excellent heat resistance, and excellent weather resistance.
  • the present invention relates to a production method, a resin coating having a cured resin layer of the coating resin composition on a surface of the base material, and a production method thereof.
  • hydrolyzable organo A coating agent obtained by hydrolyzing or partially hydrolyzing silane or a coating agent obtained by mixing a colloidal silicide force with the coating composition is known.
  • JP-A-51-2736, JP-A-51-2737, JP-A-53-130732, and JP-A-63-168470 disclose organoalkoxysilanes and hydrolysis of the organoalkoxysilanes.
  • a coating agent comprising a product and / or a partial condensate thereof and colloidal silica and converting an alkoxy group into silanol with excess water has been proposed.
  • the coating film obtained by these coating agents has high hardness, good weather resistance and is excellent for protecting the base material, but has poor toughness, and in a coating film with a film thickness of 10 m or more, Cracks easily occur during heat curing, when used outdoors, and when a sudden temperature change occurs.
  • the coating film obtained with these coating agents requires high-temperature heating of about 100 ° C or more or long-time heat treatment to obtain the desired coating film properties. Or, there was an inconvenience that it could not be used in some places such as outdoors.
  • these coating compositions have a problem in that silanols obtained by hydrolysis of alkoxysilanes have high reactivity, and their condensation reaction occurs gradually even at room temperature, easily gelling, and having poor stability. there were. In particular, when these coating compositions are used as vehicles and pigments are added to form coatings, the stability is further deteriorated, and there is a drawback that coatings cannot be formed.
  • a coating agent which converts water to a partial hydrolyzate or partial condensate of an alkoxysilane and a catalyst as a curing agent immediately before coating to convert an alkoxy group into a silanol. ing.
  • this coating agent also has poor toughness, and cracks easily occur at a film thickness of 10 m or more.
  • this coating agent has good storage properties and is relatively stable even when it is made into a paint by adding a pigment. It cannot be used depending on the molding method and dimensions of the base material, heat resistance, or places such as outdoors.
  • Japanese Patent Application Laid-Open No. 63-268772 proposes a coating agent which is composed of a prepolymer mainly composed of a gay alkoxide, a curing catalyst and water, and which can be cured at around room temperature.
  • the toughness has not been improved, and it is not possible to perform processing after painting Breccoat metal or processing after coating of polycarbonate plates.
  • the paintability and curability were poor, and the curability of the coating agent was easily affected by humidity.
  • Japanese Patent Application Laid-Open No. 4-175388 discloses a coating agent containing a partially hydrolyzed oligomer of an organosilane, a polyorganosiloxane containing a silanol group, and a curing catalyst.
  • a coating agent based on organoalkoxysilanes or hydrolysates of organoalkoxysilanes have high hardness, are resistant to scratching, and have high weatherability.
  • due to poor toughness cracks are likely to occur in the painting process or during use, especially when the film thickness exceeds 10 m.
  • baking at a high temperature of 100 ° C or more is required, and painting at factories is possible, but painting outdoors and on-site is difficult.
  • Another drawback is that the paint liquid has high reactivity and is inferior in paint storability.
  • a resin having an organic resin such as acrylic, polyester, epoxy, polyether, or vinyl in a main chain and having a hydrolyzable silane functional group has been reported.
  • the main chain is an organic resin
  • the weather resistance and the hardness are lower than those of a resin containing an organoalkoxysilane as a main component.
  • a reactive resin having a linear polysiloxane in the main chain and having a polymerizable acrylic functional group at a terminal or a side chain has also been proposed in JP-A-5-72928 and JP-A-5-178998. ing.
  • the main chain is a linear polysiloxane
  • the hardness is not obtained, and in some cases, it is a rubber elastic body, which is not suitable as a coating resin.
  • the above-mentioned concrete / cement base material and hardened inorganic material are materials with excellent heat resistance and durability, but if the surface is not painted, moisture will infiltrate, and it will be poor in stain resistance and acid resistance. There are drawbacks. Furthermore, the unpainted appearance is often not aesthetic.
  • organic paints In order to make up for these drawbacks, an organic paint has been coated on the surface.
  • organic paints have the disadvantages that they have poor weather resistance and are easily damaged due to low film hardness.
  • An object of the present invention is to form a coating film having not only high hardness and weather resistance but also high toughness, no cracks even at a film thickness of 10 zm or more, and curing and drying at room temperature is possible. It can be cured by accelerated heating at a low temperature of 100 or less, has good storage stability, and can provide the above-mentioned high-performance coatings stably for more than one year.
  • a resin composition for coating that can be used as a stable vehicle and can be arbitrarily colored by adding a pigment, a method for producing the same, and a resin coating having a cured resin layer of the resin composition for coating on the surface of a substrate And a method of manufacturing the same.
  • B 1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms or fujyl group, n is an integer of 0 to 3, X is a hydrolyzable functional group A) an organosilane silica-dispersed oligomer solution obtained by partially hydrolyzing the hydrolyzable organosilane represented by the formula in colloidal silica dispersed in an organic solvent, water or a mixed solvent thereof;
  • E 2 represents a hydrogen atom or a methyl group.
  • At least one first acrylate or methacrylate represented by the formula is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms
  • K 3 in the formula is an epoxy group, a glycidyl group or at least one second acrylate or methacrylate which is a hydrocarbon group containing the same, and represented by the general formula (II),
  • B 3 in the formula is at least one tertiary aryl group which is a hydrocarbon group containing an alkoxysilyl group or a halogenated silyl group.
  • Acrylic resin which is a copolymer with acrylate or methacrylate
  • the component (A) is obtained by partially hydrolyzing the hydrolyzable organononran under the condition of using 0.001 to 0.5 mol of water per 1 equivalent of the hydrolyzable functional group (X). It is preferable that the solution is a solution of a luganosilane in a silicic force-dispersed oligomer.
  • component (A) preferably contains 5-95 wt% silica content (weight obtained by converting the content Si on Si0 2) as a solid.
  • the pH of the component (A) is preferably from 2.0 to 7.0.
  • the acryl resin of the component (B) is a copolymer monomer comprising at least one selected from the group consisting of n-butyl methacrylate and n-butyl acrylate, trimethoxysilylpropyl methacrylate and trimethoxy. Copolymers containing at least one member selected from the group consisting of silylpropyl acrylate and at least one member selected from the group consisting of glycidyl methacrylate and glycidyl acrylate It is preferred that
  • the acrylic resin as the component (B) may further contain at least one selected from the group consisting of thiols, thiophenols and derivatives thereof.
  • the acrylic resin as the component (B) preferably has a weight average molecular weight in terms of polystyrene of from 1,000 to 50,000, and more preferably from 1,000 to 12,000.
  • the resin composition for coating of the present invention 1 to 99 parts by weight of the component (A) and 1 to 99 parts by weight of the component (B) (however, the total of the components (A) and (B) is Is 100 parts by weight).
  • the curing catalyst of the component (C) is an alkyl titanate, a tin carboxylate, an aluminum compound, an amine salt, an amine silane coupling agent, a halogenated sila It is preferably at least one member selected from the group consisting of carboxylic acids, acids and alcohols.
  • a polyorganosiloxane having a silanol group in the molecule is further contained as an essential component.
  • the coating resin composition further containing the component (D), 5 to 50 parts by weight of the component (B) and 1 to 94 parts by weight of the component (D) based on 1 to 94 parts by weight of the component (A). (However, the total of component (A), component (B) and component (D) is 100 parts by weight).
  • the weight average molecular weight in terms of polystyrene of the component (D) is preferably from 700 to 20,000.
  • the coating resin composition of the present invention may further contain (E) a pigment as an essential component.
  • the resin composition for coating according to the present invention is a two-pack type composed of a resin solution containing the component (A) and the component (B) and a resin solution containing the component (C). In mixing, use both.
  • the resin solution containing the component (A) and the component (B) and the resin solution containing the component (B) may be mixed and used.
  • the resin solution containing the component (A) and the resin solution containing the component (B) and the component (C) may be mixed and used.
  • a resin solution containing the component (A), the component (B) and the component (C), and a resin solution containing the component (D) are used.
  • Mix The resin solution containing the component (A) and the component (C) and the resin solution containing the component (B) and the component (D) may be used in combination. it can.
  • a resin solution containing the component (A), the component (B) and the component (C), and a resin solution containing the component (C) and the component (D) may be mixed and used. Good.
  • the resin coating according to the present invention has a cured resin layer of the coating resin composition according to the present invention on the surface of a substrate.
  • the resin coating according to the present invention may optionally have two or more resin layers on the surface of the base material, in which case at least one of these resin layers is used. It is a cured resin layer of the resin composition for coating according to the present invention.
  • the resin coating according to the present invention preferably further has a primer layer as a first layer between the substrate and the resin layer.
  • the primer layer has a solid content of at least one selected from the group consisting of an epoxy resin, an acrylic resin, an acrylic silicone resin, a chlorinated rubber resin, a urethane resin, a fuanol resin, a polyester resin, and a melamine resin in a solid content of 10% by weight or more. It is preferably a cured resin layer of the primer composition to be contained.
  • (b-1) 1 to 100 parts by weight of an organic gay compound having at least one mercapto group and at least two alkoxyl groups in one molecule,
  • the isocyanate group contained in the component (a-1) is not directly bonded to a benzene ring.
  • the braima layer, (a-2) 99.5 to 75 mol% of an ethylene type monomer and a general formula BSiJL ⁇ ′ ( 3 m )
  • R represents a monovalent hydrocarbon group including a vinyl group
  • R ′ is X represents a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • X is a group consisting of an alkoxyl group having 1 to 4 carbon atoms, an alkoxyalkoxyl group having 2 to 6 carbon atoms, and an oxime group having 2 to 4 carbon atoms.
  • the primer layer may contain a pigment, if necessary.
  • At least one of the resin layers may be a cured resin layer having a pattern formed by dividing and / or Z-coating a resin composition containing at least two kinds of pigments.
  • At least one of the resin layers is a cured resin of a coating resin composition containing at least one pigment, and a cured resin layer of a pigment-free coating resin composition is formed on the cured layer. It may be formed.
  • the resin coating according to the present invention may be subjected to at least one of bending, drawing, punching, punching, cutting, and pressing.
  • the base material is preferably a steel plate, a non-ferrous metal, an inorganic cured product, glass, plastic, or wood.
  • the inorganic cured product preferably has a bulk density of 0.5 g / cm 3 or more, and its dimensional change from saturated water absorption to absolute drying is preferably 0.5% or less.
  • the inorganic cured material may have a tongue-processed portion and / or an uneven pattern, if necessary.
  • the method for producing a resin coating according to the present invention includes a step of forming at least one resin layer on a surface of a substrate. At least one of the resin layers according to the present invention After coating the resin composition for coating on the surface of the base material, the resin composition for coating is formed by curing the resin composition for coating.
  • the method for producing a resin coating according to the present invention includes coating the primer composition on the surface of the substrate before forming the resin layer, and curing the primer composition to form the resin composition.
  • the method may further include a step of forming a primer layer as a first layer on the surface.
  • the method for producing a resin coating according to the present invention may include forming the primer layer and the resin layer or the resin layer on the surface of the base material, and then bending, drawing, punching, punching, and cutting.
  • the method may further include a step of performing at least one of processing and press processing.
  • the method for producing a resin coating according to the present invention may further include a step of forming at least one resin layer after performing the processing.
  • the base material is preferably a steel plate, a non-ferrous metal, an inorganic cured product, glass, plastic, or wood.
  • the inorganic cured product preferably has a bulk density of 0.5 g / cm 3 or more, and its dimensional change from saturated water absorption to absolute drying is preferably 0.5% or less.
  • the inorganic cured material may have a tongue-processed portion and / or an uneven pattern, if necessary.
  • FIG. 1 is a plan view showing an example of a processed inorganic cured product used in the present invention.
  • FIG. 2 is a cross-sectional view showing an uneven portion of the processed inorganic cured product of FIG.
  • the resin composition for coating according to the present invention contains the component (A), the component (B) and the component (C) as essential components, and further contains the component (D) as necessary.
  • the silica-dispersed oligomer of the component (A) is a main component of a base polymer having a hydrolyzable group (X) as a functional group that is subjected to a curing reaction when forming a coating film.
  • a hydrolyzable group (X) as a functional group that is subjected to a curing reaction when forming a coating film.
  • This Refers to colloidal silica dispersed in an organic solvent or water (including a mixed solvent of an organic solvent and water) and one or more of the hydrolyzable organosilanes represented by the general formula (I). And hydrolyzable organosilane is partially hydrolyzed with water in colloidal silica or separately added water.
  • the group in the hydrolyzable organonone run represented by the general formula (I) !? 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 9 carbon atoms, for example, a methyl group, an ethyl group, Alkyl groups such as propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group, 2-phenylylpropyl group, Aralkyl groups such as 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and acryl group; chloromethyl group, archloropropyl group, 3,3,3- Halogen-substituted hydrocarbon groups such as trifluoropropyl; ⁇ -methacryloxypropyl, 7-
  • an alkoxy group is preferable because of its easy availability and easy preparation of a silicic acid-dispersed organosilane oligomer solution.
  • hydrolyzable organosilanes examples include mono-, di-, tri-, and tetra-functional alkoxysilanes, acetoxysilanes, and oximesilanes in which n in the general formula (I) is an integer of 0 to 3. , Enoxysilanes, aminosilanes, aminoxysilanes, amidonlanes and the like. Among them, easy availability and easy preparation of silicic acid-dispersed organosilane oligomer solution And alkoxysilanes are preferred.
  • Examples of the silane include trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl isopropoxy silane, dimethyl isobutyl methoxy silane, and the like.
  • the colloidal silica in the component (A) is necessary for increasing the hardness of the coating film of the coating resin composition of the present invention.
  • Such colloidal silica is water-dispersible (I), and organic solvent dispersible colloidal silica can be used.
  • colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value.
  • water-dispersible colloidal silica water present as a component other than the solid content can be used for hydrolyzing the hydrolyzable organosilane of the component (A). These are usually made from water glass, but such colloidal silicides are readily available commercially.
  • the organic solvent-dispersed colloidal silica can be easily prepared by replacing water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent dispersible colloidal silica can be obtained as a commercial product in the same manner as the water dispersible colloidal silica.
  • Colloida Types of organic solvents in which silica is dispersed include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol: ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl acetate.
  • Ethylene glycol derivatives such as ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol.
  • ether diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether
  • diacetone alcohol One or a mixture of two or more selected from the group consisting of these are used. be able to.
  • Toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone oxime, and the like can also be used in combination with these hydrophilic organic solvents.
  • colloidal silica in a component, colloidal silica, silica content (weight obtained by converting the content Si on Si0 2) as a solid, preferably 5-9 5% by weight, more preferably 2 0-8 5 weight range It is contained in. If the content is less than 5% by weight, the desired coating film hardness cannot be obtained, and if it exceeds 95% by weight, it becomes difficult to uniformly disperse the silica, and the component (A) may gel.
  • the silica-dispersed oligomer of the component (A) can be obtained by partially hydrolyzing the hydrolyzable organosilane represented by the general formula (I) in water-dispersed colloidal silica or colloidal silica dispersed in an organic solvent.
  • the amount of water to be added to the hydrolyzable organosilane is preferably 0.001 to 0.5 mol per 1 equivalent of the hydrolyzable group (X). If the ratio is less than 0.001 mol, sufficient hydrolyzate cannot be obtained, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate deteriorates.
  • the method of performing the partial hydrolysis is not particularly limited, and the hydrolyzable organosilane and colloidal silica may be mixed and a necessary amount of water may be added, and the partial hydrolysis reaction proceeds at room temperature.
  • An organic acid and an inorganic acid such as an acid, toluenesulfonic acid, and oxalic acid may be used as the catalyst.
  • the component (A) preferably has a pB of the solution of 2.0 to 7.0, more preferably 3.0 to 6.0, in order to obtain long-term storage stability. If the pH is out of this range, the long-term storability of the component (A) may be significantly deteriorated, particularly under the condition that the amount of water used is 0.3 mol or more with respect to XI equivalent.
  • the pH of the component (A) is outside the above range, the pH may be adjusted by adding a basic reagent such as ammonia or ethylenediamine if the pH is more acidic than the above range.
  • the pH may be adjusted by using an acidic reagent such as hydrochloric acid, nitric acid, or oxalic acid.
  • the adjustment method is not particularly limited.
  • the acrylic resin as the component (B) is an important component having an effect of improving the toughness of a coating film obtained from the coating resin composition of the present invention, and the first resin represented by the general formula (II) , And second and third acrylates or methacrylates.
  • the first acrylic acid ester or methacrylic acid ester is a substituted or unsubstituted monovalent hydrocarbon group in which B 3 in the formula (II) has 1 to 9 carbon atoms, for example, methyl group, ethyl group, n-propyl Groups, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and other alkyl groups; cyclopentyl group, cyclohexyl group Cycloalkyl groups such as xyl groups: aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group, and 3-funylpropyl group; aryl groups such as phenyl group and tolyl group; chloromethyl group; At least one of the following groups: a halogenated hydrocarbon group
  • the third acrylate or methacrylate is a hydrocarbon group in which E 3 in the formula (II) contains an alkoxysilyl group or a halogenated silyl group, for example, a trimethoxysilylpropyl group, a dimethoxymethylsilylpropyl group.
  • E 3 in the formula (II) contains an alkoxysilyl group or a halogenated silyl group, for example, a trimethoxysilylpropyl group, a dimethoxymethylsilylpropyl group.
  • the component (B) is a copolymer of acrylate or methacrylate containing at least one of each of the first, second, and third acrylates or methacrylates in total.
  • the first acrylate or methacrylate is an essential component for improving the paddy properties of the coating film, and further has an effect of improving the compatibility of the components (A) and (D). is there.
  • the substituted or unsubstituted hydrocarbon group of R 3 preferably has a certain volume or more, and preferably has 2 or more carbon atoms.
  • the second acrylate or methacrylate is an essential component for improving the adhesion of the coating film to the substrate.
  • the third acrylate or methacrylate forms a chemical bond between the component (B) and the component (A) and optionally the component (D) when the coating film is cured.
  • the components are fixed in the coating film.
  • the third acrylate or methacrylate also has an effect of improving the compatibility between the component (B) and the component (D) and optionally the component (D).
  • the molecular weight of the acrylic resin as the component (B) greatly affects the compatibility with the component (A) and the optional component (D).
  • the weight average molecular weight of the acrylic resin (B) in terms of polystyrene exceeds 50,000, phase separation may occur and the coating film may be whitened. Accordingly, it is desirable that the weight average molecular weight in terms of polystyrene of the acrylic resin of the component (B) be 50,000 or less, preferably 12,000 or less.
  • the lower limit of the weight average molecular weight in terms of polystyrene of the acrylic resin as the component (B) is desirably 1,000.
  • the second acrylate or methacryl having an epoxy group is desirably 2 or more in terms of monomer molar ratio in the copolymer. If it is less than 2%, the adhesion of the coating film will be insufficient.
  • the third acrylate or methacrylate having an alkoxysilyl group or a halogenated silyl group is desirably in the range of 2 to 50% in terms of a monomer molar ratio in the copolymer.
  • the compatibility between the component (B) and the component (A) and the component (D) used as required is poor, and the coating film may be whitened.
  • it exceeds 50 ° C the bond density of the component (B) with the component (A) and the component (D) used as required becomes too high, and the improvement of toughness, which is the original purpose of the component (B), is not achieved. can not see.
  • the method for synthesizing the component (B) includes a radical polymerization method based on solution polymerization, emulsion polymerization, or suspension polymerization in a known organic solvent, or an anion polymerization method or a cationic polymerization method. Absent.
  • the first, second, and third acrylate or methacrylate monomers are dissolved in an organic solvent in a reaction vessel by a known method, and the radical polymerization is further performed. Add initiator and heat under nitrogen stream to react.
  • the organic solvent is not particularly limited, for example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl acetate Ether and the like are used.
  • the radical polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetylacetyl peroxide, lauroyl peroxide, Azobisuisopuchi Ronitoriru, hydrogen peroxide - Fe 2 + salt, persulfate - NaBS0 3, cumene O carboxymethyl -Fe 2 + salts, peroxides base emission zone I Lou dimethyl ⁇ diphosphoric, peroxides one Bok Riechiruaru Minimum is used.
  • a chain transfer agent can be added.
  • chain transfer agent examples include, but are not limited to, quinones such as monoethyl hydroquinone and P-benzoquinone; mercaptoacetic acid ethyl ester; mercaptoacetic acid n— Thiols such as butyl ester, mercaptoacetic acid 2-ethylhexyl ester, mercaptocyclohexane, mercaptocyclopentane, 2-mercaptoethanol; di-3-chlorobenzene thiol, P- Thiophenols such as toluene thiol and benzene thiol; thiol derivatives such as amercaptopropyl trimethoxysilane; phenylbiacrylhydrazine; diphenylamine; tertiary butyl catechol and the like can be used.
  • quinones such as monoethyl hydroquinone and P-benzoquinone
  • the curing catalyst which is the component 0, promotes the condensation reaction of the component (A), the component (B), and the component (D) used as required, and cures the coating film.
  • alkyl titanates such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate Quaternary ammonium salts of carboxylic acids, such as tetramethylammonium acetate; amines, such as tetraethylpentamine; and amine-based silane cups, such as N-yS-aminoethyl-aminopropyl pyrmethyldimethoxysilane.
  • Ring agent P-toluenesulfonic acid, phthalic acid, hydrochloric acid, and other acids; aluminum alkoxide, aluminum chelate
  • aluminum catalysts such as lithium hydroxide
  • titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetyl acetate
  • halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane
  • the silanol group-containing polyorganonoxane of the component (D) used as required is represented by the above average composition formula ( ⁇ ), and undergoes a condensation reaction with the components (A) and (B) to form a cured coating film. It is a component that further improves the smoothness, mechanical strength, and toughness of the coating film.
  • Examples of E 4 in the formula ( ⁇ ) include the same as R 1 in the formula (I), and preferably include an alkyl group having 1 to 4 carbon atoms, a phenyl group, a butyl group, an aglycidoxypropyl group, E.g., aminopropyl, 3,3,3-trifluoropropyl, etc.
  • a and w are numbers satisfying the above-mentioned relationship, respectively.
  • a is less than 0.2 or b exceeds 3, cracks are liable to occur in the cured coating film.
  • a is more than 2 and 4 or less, or when b is less than 0.0001, curing does not proceed.
  • Such silanol group-containing polyorganosiloxanes include, for example, one or a mixture of two or more of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyltrichlorosilane, and corresponding alkoxysilanes. It can be obtained by hydrolysis with a large amount of water according to the method described above.
  • a silanol group-containing polyorganosiloxane is hydrolyzed by a known method using alkoxysilane, unhydrolyzed alkoxysilane may remain. That is, a polyorganosiloxane in which a silanol group and an alkoxy group coexist may be obtained. In the present invention, such a polyorganosiloxane may be used.
  • the weight average molecular weight in terms of polystyrene of the silanol group-containing polyorganosiloxane (D) is preferably from 700 to 20,000. If the molecular weight is lower than this range, the toughness of the coating film tends to be low and cracks are likely to occur, while if the molecular weight is higher than the above range, the resin in the coating film tends to phase separate and whiten. Is not preferred.
  • the mixing ratio of the component (A) and the component (B) is preferably 1 to 99 parts by weight of the component (A), 99 to 1 part by weight of the component (B), 5 to 95 parts by weight of the component (A), and (B)
  • the component is more preferably 95 to 5 parts by weight (provided that the total of the component (A) and the component (B) is 100 parts by weight). Also in this case, when the component (A) exceeds 99 parts by weight, cracks tend to occur in the coating film, and when it is less than 1 part by weight, the hardness of the coating film cannot be obtained.
  • the mixing ratio of the component (A), the component (B), and the component (D) is 1 to 94 parts by weight of the component (A) and 5 to 5 parts by weight of the component (B). 50 parts by weight, preferably 1 to 94 parts by weight of component (D), more preferably 20 to 94 parts by weight of component (A), 5 to 50 parts by weight of component (B), and more preferably 20 to 94 parts by weight of component (D). However, the total of the components (A), (B) and (D) is 100 parts by weight.) If the component (A) exceeds 94 parts by weight, the coating film will crack. If it is less than 1 part by weight, the hardness of the coating film cannot be obtained. If the component (B) exceeds 50 parts by weight, the weather resistance of the coating film cannot be obtained, and if it is less than 5 parts by weight, sufficient toughness cannot be obtained.
  • Component (C) should be added in an amount of 0.001 to 10 parts by weight, based on 100 parts by weight of component (A), component (B) and optional component (D). . If it is less than 0.001 parts by weight, it may not cure at room temperature, and if it exceeds 10 parts by weight, heat resistance and weather resistance may be deteriorated.
  • the coating resin composition of the present invention can be made into a paint by adding a pigment.
  • Pigments to be added are preferably organic pigments such as carbon black, quinacridone, naphthol red, shinyble, cyanine green, Hansa Yellow, and inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxide.
  • organic pigments such as carbon black, quinacridone, naphthol red, shinyble, cyanine green, Hansa Yellow
  • inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxide.
  • the amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment, but is not limited to 100 parts by weight of the total solid content of the component (A), the component (B), and the component (D) used as required. And preferably 5 to 80 parts by weight. When the amount is less than 5 parts by weight, the concealing property is poor.
  • the dispersion of the pigment may be performed by a usual method. At that time, it is possible to use dispersants, dispersing aids, thickeners, coupling agents and the like.
  • the thickness of the coating film is not particularly limited, and may be 0.1 to 100. However, in order for the coating film to be stably adhered and held for a long term without cracking or peeling, 1 to 50 // m is preferred.
  • the coating resin composition of the present invention can be coated by a normal coating method.
  • various coating methods such as brush coating, spraying, immersion, flow, roll, curtain, and naf coat can be selected. it can.
  • the dilution ratio in the organic solvent is not particularly limited, and may be determined as needed.
  • the resin composition for coating of the present invention may contain, as necessary, a leveling agent, a thickener, a pigment, a dye, an aluminum paste, a glass frit, a gold powder, an antioxidant, an ultraviolet absorber, and the like. Can be added in a range that does not adversely affect the effect of You.
  • the coating resin composition of the present invention is preferably used as a two-pack type resin composition, and examples thereof include the following methods (1), (2) and (3).
  • a resin solution containing the component (A) and the component (B) is mixed with a resin solution containing the component (C).
  • a resin solution containing the component (A) and the component (C) is mixed with a resin solution containing the component (B).
  • the resin composition for coating of the present invention further contains the component (D)
  • the resin composition for coating can be used as the following two-pack type composition. For example, the following (4), (5) ) Or (6).
  • a resin solution containing the component (A), the component (B) and the component (C) is mixed with a resin solution containing the component (D).
  • a resin solution containing the component (A) and the component (C) and a resin solution containing the component (B) and the component (D) are mixed.
  • a more specific method of mixing the components is not particularly limited.
  • the component (A) may be used.
  • the resin solution containing the component (B) was mixed with the resin solution containing the component (B), and then the resin solution containing the component (C) was further mixed (here, after mixing, the mixture was heated at 60 ° C. The reaction can be promoted), and a method of further mixing the resin solution containing the component (D).
  • This resin coating has a cured resin layer of the resin composition for coating according to the present invention on the surface of the substrate.
  • the thickness of the cured resin layer is not particularly limited and may be 0.1 to 100 m. However, in order for the cured resin layer to be stably adhered and held for a long term without cracking or peeling, the thickness is 1 ⁇ 50 ⁇ m is preferred.
  • the resin coating according to the present invention may have two or more resin layers on the surface of the base material, if necessary. In that case, at least one of these resin layers may be a cured resin layer of the coating resin composition according to the present invention. That is, it is not necessary that all of the two or more resin extensions are the cured resin layer of the coating resin composition of the present invention. A cured resin layer of the resin composition for a single layer may be mixed.
  • the resin composition for coating other than the present invention that can be used is not particularly limited, and examples thereof include phthalic acid resin enamel (eg, Nippon Paint's UNIVAC 200), polyurethane resin paint (eg, tow) Beurethane 100, etc.), and acrylic resins (eg, Kansai Paint AP Enamel, etc.). These are used, for example, for the purpose of protecting an organic coating film having poor weather resistance and low film hardness, and imparting design properties to the coating film of the coating resin composition of the present invention with an organic paint.
  • phthalic acid resin enamel eg, Nippon Paint's UNIVAC 200
  • polyurethane resin paint eg, tow
  • acrylic resins eg, Kansai Paint AP Enamel, etc.
  • the thickness of the cured resin layer of the coating resin composition other than the present invention is not particularly limited, but is preferably from 0.1 to 100 tx m, and more preferably from l to 50 m. If it is less than 0. l / m, there are problems such as difficulty in obtaining a uniform coating film and poor concealability. If it exceeds 100 / m, there is a problem that cracks are easily generated in the coating film.
  • the resin coating according to the present invention further comprises a first layer of a primer between the substrate and the resin layer (when there are a plurality of resin layers, the lowermost layer). It is preferred to have.
  • the thickness of the primer layer is not particularly limited, but is preferably 0.1 to 50 m, more preferably 0.5 to 10 / zm. If the thickness is too small, there are problems such as difficulty in obtaining a uniform coating film. If the thickness is too thick, foaming may occur during drying.
  • the primer layer for example, at least one selected from the group consisting of an epoxy resin, an acrylic resin, an acrylic silicone resin, a chlorinated rubber resin, a urethane resin, a phenol resin, a polyester resin, and a melamine resin is used as a solid content. And a cured resin layer of a primer composition containing 10% by weight or more.
  • the primer layer is not limited to the above.
  • the primer layer is not limited to the above.
  • (b-1) an organic gay compound having at least one mercapto group and at least two alkoxyl groups in one molecule 1 to: 100 parts by weight;
  • the isocyanate group contained in the component (a-1) is preferably not directly bonded to a benzene ring when it is required that the color is not changed by light.
  • component (a-1) are not particularly limited, but include, for example, hexmethylenediocyanate, tolylenediocyanate, m-xylylenediocyanate, and tris (2-hydroxydene).
  • the present application does not contain a urethane bond and that the isocyanate group is not directly bonded to the benzene ring.
  • the organic gayne compound as the component (b-1) is a silane coupling agent having a mercapto group that reacts with the organic compound and an alkoxy group that reacts with the inorganic compound, and acts as an adhesive improving agent.
  • organic Gay-containing compounds particularly limited by a bur, for example, HS (CH 2) 3 Si (0CH 3) 3, HS (CB 2) 3 Si (0C 2 H 5) 3, HS ( CB 2) 2 Si (0CH 3 ) s, BS (CH 2) 2 Si (0C 2 B 5) 3, HS (CH 2) 3 Si (CH 2) (0CH 3) silane and their 2 such hydrolysis Objects and the like. These may be used alone or in combination of two or more.
  • the component (b-1) is added in an amount of 1 to 100 parts by weight, preferably 3 to 100 parts by weight, based on 100 parts by weight of the isocyanate prepolymer of the component (a-1). 550 parts by weight. If the proportion is less than 1 part by weight, the adhesiveness may not be sufficiently exhibited, and the strength of the coating may be poor. If the proportion exceeds 100 parts by weight, the adhesiveness tends to be rather reduced.
  • the epoxy resin-modified silicone resin as the component (c-1) contributes to the improvement of the adhesion and the ultraviolet resistance of the primer.
  • the epoxy resin component is a low-molecular or polymer containing a compound having an oxysilane oxygen such as a glycidyl group or a 3,4-oxycyclohexyl group, and various acid anhydrides and amines are used as a curing agent. You may.
  • the curing agent component is not particularly limited, and examples thereof include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, dodecyl succinic anhydride, and the like. Alternatively, a plurality of types are used in combination.
  • the compounding amount of the epoxy resin-modified silicone resin of the component (c-1) is 100 parts by weight or less as a solid component based on 100 parts by weight of the isocyanate prepolymer of the component (a-1). And preferably 3 to 50 parts by weight. If the above proportion exceeds 100 parts by weight, not only the weather resistance and the adhesiveness may be impaired, but also the stability of the primer liquid is not preferred.
  • the organic tin compound and / or tin organic acid salt of the component (d-1) serves as a reaction catalyst for an isocyanate group, an alkoxysilyl group, a silanol group, and the like contained in other primer components.
  • tin compounds are not particularly limited, but include tin carboxylate such as tin octylate, dibutyltin acetate, dibutyltin laurate, dibutyltin Organotin carboxylate salts such as tin malate and dibutyltin phthalate, and deesterification reaction products of these compounds with alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; organic tin oxides such as dibutyltin oxide; A reaction product with the ester can be exemplified.
  • the compounding amount of the component (d-1) is 0.01 to 30 parts by weight, preferably 0.00 part by weight, based on 100 parts by weight of the isocyanate prepolymer of the component (a-1). 5 to -10 parts by weight. If the amount is less than 0.01 part by weight, the adhesiveness, particularly the water resistance of the adhesive, may decrease.If the amount exceeds 30 parts by weight, the curing speed of the primer composition becomes too high. However, there is a tendency that a problem occurs in the application workability.
  • the primer composition composed of the above components is appropriately diluted with an organic solvent for the purpose of facilitating the coating operation and for imparting storage stability.
  • organic solvent examples include, for example, carboxylic acid esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic compounds such as toluene, xylene and benzene.
  • Ethers such as getyl ether, tetrahydrofuran and dioxane, or oxygen-containing heterocyclic compounds and the like can be used. These solvents may be used alone or in combination of two or more.
  • the primer hiring is also not limited to the above, for example,
  • It may be a cured resin layer of a primer composition containing as an essential component.
  • the ethylene monomer as a raw material of the component (a-2) is not particularly limited, For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethyl Alkyl (meth) acrylates such as hexyl acrylate; conjugated gens such as styrene, vinyl toluene, and methyl styrene; vinyl esters of saturated fatty acids having 1 to 12 carbon atoms such as vinyl acetate and vinyl propionate; Can be mentioned.
  • the monovalent hydrocarbon group R containing a vinyl group may be vinyl.
  • Acryl, 3-acryloxypropyl, 3-methacryloxypropyl, P-vinylphenyl, etc. are recommended because of availability of raw materials and ease of synthesis.
  • the hydrolyzable group X include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, P-propoxy, and n-butoxy; and 2 to 6 carbon atoms such as methoxetoxyl and ethoxyquin etkinl.
  • the number m of the hydrolyzable group X is selected from an integer of 1 to 3, and is preferably 2 or 3, and particularly preferably 3 in order to form a network structure in a short time.
  • Specific examples of these unsaturated group-containing silicon compounds are not particularly limited, but include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (ethoxyethoxy) silane, vinyltris (methylethylketoxime) silane, and aryltrime.
  • Toxin orchid aryltriethoxyquin silane, arinoretris (methylethyl ketoxime) silane, 3-acryloxypropyl trimethoxy silane, 3-acrylyl propyl triethoxy silane, 3-acryloxy propyl tris (ethoxy ethoxy) silane, 3-acryloxypropyl tris (methylethyl ketoxime) silane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl tris ( Tokishietokin) silane, 3-Metakurirokishibu opening Birutorisu (Mechiruechiruke Toxime) silane and the like.
  • the hydrolyzable group-containing vinyl copolymer of the component (a-2) is obtained by combining the above-mentioned ethylenic monomer and the unsaturated group-containing gayne compound, for example, in the presence of an organic solvent and a free radical initiator. , 50 to: obtained by reacting at a temperature of 150.
  • the free radical initiator is not particularly limited.
  • an azo compound or an organic peroxide can be used. Tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, tert-butyl perbenzoate, acetone peroxide, and the like.
  • the amount of the free radical initiator is not particularly limited, it is suitably 0.01 to 1% by weight based on the total amount of the ethylenic monomer and the unsaturated group-containing gayne compound.
  • a chain transfer agent such as n-propanethiol, 1-hexanethiol, 1-decanethiol, benzenethiol, 3-mercaptopyl biltrimethoxysilane, or 3-mercaptoprovirtriethoxysilane is used.
  • the ratio of the ethylene monomer to the unsaturated group-containing gay compound is 99.
  • the content of the unsaturated group-containing gay compound is 0.5 to 25 mol% to 5 to 75 mol%. If the amount of the unsaturated group-containing gay compound is less than this range, the weather resistance of the coating film is unfavorably reduced, and if it is more than this range, one layer of the primer becomes brittle.
  • the epoxy resin-modified silicone resin of the component (b-2) is not particularly limited, and examples thereof include the same as the epoxy resin-modified silicone resin of the component (c-1).
  • the amount of the epoxy resin-modified silicone resin used as the component (b-2) is 0 parts by weight based on 100 parts by weight of the hydrolyzable group-containing vinyl copolymer as the component (a-2). It is desirable that the amount be 1 to 50 parts by weight. If the amount used is less than 0.1 part by weight, the weather resistance and the toughness of the film may be impaired. If the amount exceeds 50 parts by weight, the adhesiveness is undesirably reduced.
  • the primer composition containing the component (a-2) and the component (b-2) may be, if necessary, A curing catalyst may be further included.
  • the amount of the curing catalyst used is preferably less than 20 parts by weight based on 100 parts by weight of the vinyl copolymer having a hydrolyzable group. If the amount is more than 20 parts by weight, it exudes to the surface of the primer coat and the adhesiveness is hindered.
  • the curing catalyst include, but are not particularly limited to, dibutyltin laurate, dibutyltin acetate, butyltin tri (2-ethylhexoate), stannous caprylate, tin naphthenate, tin oleate, Iron 2-ethylhexoate, Lead 2-ethyloxoate, Cobalt-2-ethylhexoate, Manganese 2-ethylhexoate, Zinc 1-2-ethylhexoate, Titanium naphthenate, Zinc naphthenate, Naphthenic acid Metal salts of organic carboxylic acids such as cobalt and zinc stearate; organic titanates such as tetrabutyl titanate and tetra (isoprobenyloxy) titanate; organotitanium quintitanium; and organic titanium compounds such as 9-strength luponyltitanium; Piltriethoxys
  • any of the above-mentioned primer compositions may further contain other additives such as coloring pigments such as titanium oxide, carbon black and iron oxide, if necessary.
  • the method for applying the primer composition is not particularly limited, and for example, brush coating, spraying, a roll coater, flowco overnight, and the like can be used, and the coating film thickness is preferably 0.5 to 10 m. Dry curing is not particularly limited, but for example, treatment can be performed in a dryer at 80 ° C for 10 to 20 minutes.
  • At least one of the resin layers is a resin composition containing at least two kinds of pigments. It may be a cured resin layer having a pattern formed by divided coating and z or multi-layer coating.
  • At least one of the resin layers is a cured resin layer of a coating resin composition containing at least one pigment, and a cured resin layer of a pigment-free coating resin composition is formed on the cured layer. It may be formed.
  • the resin coating according to the present invention may be subjected to at least one of bending, drawing, punching, punching, cutting, and pressing.
  • This manufacturing method includes a step of forming at least one resin layer on the surface of the base material. At least one of the resin layers is formed by coating the resin composition for coating according to the present invention on the surface of the substrate and then curing the resin composition for coating.
  • the method for producing a resin coating according to the present invention may further include a step of forming a primer layer as a first layer on the surface of the substrate before forming the resin layer.
  • sealing may be performed with a solvent-based, water-soluble or emulsion-based sealer to adjust the variation in suction on the surface of the base material.
  • sealer used is not particularly limited, and acrylic, latex and the like can be used.
  • the method for producing a resin coating according to the present invention includes: forming the primer layer and the resin layer on the surface of the base material; bending, drawing, punching, punching, and cutting.
  • the method may further include a step of applying at least one of press working.
  • the method for producing a resin coating according to the present invention may further include a step of forming at least one resin layer after performing the processing.
  • the substrate include, but are not particularly limited to, for example, plastics such as polycarbonate resin, acrylic resin, and ABS resin; non-ferrous metals such as aluminum, duralumin, and copper; steel plates such as stainless steel and iron; glass; Wood; paper; wall materials such as cement and gypsum; hardened inorganic materials; and ceramics such as alumina.
  • plastics such as polycarbonate resin, acrylic resin, and ABS resin
  • non-ferrous metals such as aluminum, duralumin, and copper
  • steel plates such as stainless steel and iron
  • glass wood
  • Wood wood
  • wall materials such as cement and gypsum
  • hardened inorganic materials and ceramics such as alumina.
  • the resin composition for coating according to the present invention may be used for protecting the surface of an acrylic, alkyd, polyester, epoxy or urethane paint regardless of the substrate.
  • hydraulic adhesive material having hydraulic properties used as a raw material of the inorganic cured product.
  • one or more selected from Portland cement, blast furnace cement, blast furnace slag, calcium gayate, stone blue, etc. can be used.
  • an inorganic filler a fibrous material, or the like is blended with the adhesive material.
  • fly ash, micro silica, silica sand, etc. are used as the inorganic filler
  • inorganic fibers such as pulp, synthetic fiber, asbestos, and metal fibers such as steel fiber are used as the fibrous material. are used alone or in combination.
  • the raw material of the inorganic hardened material constituted in this way is not particularly limited after being molded by a method such as extrusion molding, cast molding, papermaking molding, and press molding. Room temperature curing is suitable.
  • the resulting cured inorganic material has a bulk density of 0.5 g / cm 3 or more, and preferably has a dimensional change from saturated water absorption to absolute dryness of 0.5% or less, more preferably Those with a foveal density of 0.7 g / cm 3 or more and a dimensional change of 0.4% or less are selected.
  • the bulk density is less than 0.5 g / cm 3 , since the primer composition and the resin composition for coating of the present invention are strongly sucked, the adhesion performance is hardly exhibited, and the appearance of the coating film is poor. There is a risk of becoming.
  • the inorganic cured product may have a tongue-processed portion and / or an uneven pattern, if necessary.
  • Examples of such inorganic cured products include the dimensions shown in Figures 1 and 2. Law (unit ⁇ ), but like that is processed into the shape and the like, c embodiment, but not limited to
  • IPA-ST isopropanol-dispersed colloidal silica sol: particle diameter 10 to 20 nm, solid content 30%, moisture 0.5%, Nissan Chemical Industries, Ltd.
  • 68 g of methyltrimethoxysilane and 2.2 g of water were added thereto, and the mixture was hydrolyzed at 65 ° C. for 5 hours while stirring, and cooled to obtain a component (A). It had a solids content of 36% when left for 48 hours at room temperature.
  • the 0 component obtained here is called A-1.
  • MA-ST methanol-dispersed colloidal silicide sol: particle size 10-20 nm, solid content 303 ⁇ 4, water content 0.5 0, Nissan Chemical Industries, Ltd.
  • MA-ST methanol-dispersed colloidal silicide sol: particle size 10-20 nm, solid content 303 ⁇ 4, water content 0.5 0, Nissan Chemical Industries, Ltd.
  • a stirrer, heating jacket, condenser and thermometer 100 g, 68 g of methyltrimethoxysilane, 49.5 g of phenyltrimethoxysilane, 16.0 g of water, and 0.1 g of acetic anhydride were added, and the mixture was hydrolyzed for 5 hours at a temperature of 60 ° C. with stirring, cooled, and the component (A) was cooled. I got It had a solids content of 41X when left at room temperature for 48 hours.
  • the component (A) obtained here is called A-2.
  • the method for preparing the component (B) is as follows.
  • N-butyl methacrylate (BMA) 5.69 g (40 mmol), trimethoxysilyl propyl methacrylate (SMA) was placed in a flask equipped with a stirrer, heating jacket, condenser, dropping funnel, nitrogen gas inlet / outlet, and thermometer.
  • SMA trimethoxysilyl propyl methacrylate
  • l. 24 g 5 mmol
  • a nitrogen stream was added to a reaction solution obtained by dissolving 0.784 g (4 mmol) of amercaptopropyltrimethoxysilane as a chain transfer agent in 8.49 g of toluene.
  • a solution prepared by dissolving 0.025 g (0.15 mmol) of azobisisobutyronitrile in 3 g of toluene was added dropwise and reacted at 70 ° C. for 2 hours.
  • a polymer having a weight average molecular weight of 1,000 was obtained, and this acrylic resin solution was directly used as the component (B). This is called B-1.
  • the molecular weight is determined by gel permeation chromatography.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • A-mercaptopropyl trimethoxysilane (0.784 g, 4niol) dissolved in 9.26 g of toluene was added dropwise to a reaction solution of 0.025 g (0.15 mmol) of azobisisobutyl nitrile in 3 g of toluene. Reacted. This is called B-2.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • HMA glycidyl methacrylate
  • 7-Mercaptoprovir trimethoxysilane 0.784 g, 4 mmol dissolved in 10.10 g of toluene was added to a reaction solution of 0.025 g of azobisisobutyronitrile (0.15 mmol) dissolved in 3 g of toluene. The mixture was dropped and reacted. This is called B-3.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • amercaptopropyl trimethoxysilane 0.784g (4mniol) dissolved in 10.90g toluene 10.90g azobisisobutyronitrile 0.025g (0.15MIO1) dissolved in 3g toluene was dropped and reacted. This is called B-4.
  • BMA n-butyl methacrylate
  • SMA trimethoxinylpropyl methacrylate
  • GMA glycidyl methacrylate
  • amercaptopropyltrimethoxysilane dissolved in 12.47 g of toluene were added to 0.025 g (0.15 ⁇ ⁇ 01) of azobisisobutyronitrile in 3 g of toluene. was dissolved and reacted. This is called B-6.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • Amercaptoprovir trimethoxysilane in a reaction solution of 0.784 g (4 mmol) dissolved in 13.27 g of toluene, and 0.025 g (0.15 ⁇ 1) of azobisisobutyronitrile dissolved in 3 g of toluene was dropped and reacted. This is called B-7.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • amercaptoprovir trimethoxysilane 0.784 g (4 mmol) of toluene dissolved in 14.06 g of toluene
  • 0.025 g of azobisisobutyronitrile 0.1 g of toluene dissolved in 3 g of toluene
  • B-8 n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • the hydrochloric acid remaining in the toluene solution of toluene is removed by washing with water, the toluene is further removed under reduced pressure, and the residue is diluted with isopropyl alcohol.
  • the isopropyl alcohol of the silanol-containing organopolysiloxane having a weight average molecular weight of about 2,000 is obtained. A 40% solution was obtained. This is called D-1.
  • a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel, and a thermometer was charged with 1,000 g of water and 50 g of acetone, and then 44.8 g (0.3 mol) of methyltrichlorosilane and 84.6 g of phenyltrichlorosilane. (0.4 mol) dissolved in 200 g of toluene was hydrolyzed while being added dropwise with stirring. After 40 minutes, the stirring was stopped, and the reaction solution was transferred to a liquid separating port and allowed to stand. Then, the lower hydrochloric acid aqueous solution separated into two layers was separated and removed.
  • toluene of the upper organopolysiloxane was removed.
  • the water and hydrochloric acid remaining in the solution were removed together with excess toluene by vacuum stripping to obtain a toluene solution of a silanol group-containing organopolysiloxane having a weight average molecular weight of about 3,000 in toluene. This is called D-2.
  • Coating resin composition as clear paint The components shown in Tables 1 to 4 were mixed in the proportions shown in the same table, and all were diluted with isopropyl alcohol to a solid content of 25% for coating. A resin composition was obtained. The obtained resin composition for coating is spray-coated on an aluminum-sprayed test piece (trade name: Ulster; manufactured by Nippon Test Panel Co., Ltd .; dimensions: 15 Omm x 7 Omm x 0.3 mm). The cured coating was applied to a thickness of 30 m and cured at a curing temperature of 100 C for 20 minutes to form a coating, and the coating properties were tested. The coating film properties were tested according to the following evaluation methods.
  • Adhesion to the substrate was evaluated by a cross-cut adhesive tape (using cellophane tape) peel test.
  • Coating film hardness By pencil hardness test (according to JIS K5400).
  • Solvent resistance Lightly press the coating with gauze soaked in toluene and rub 100 times back and forth. Observation of the state of the coating film at that time showed that there was no change, and that the cured state was good.
  • Boiling resistance After boiling water for 16 hours, the test piece was left for 1 hour and the condition of the coating film was observed.
  • the coating resin compositions of the examples were compared with the comparative examples in that the coating film had all of the following properties: adhesion, coating film hardness, solvent resistance, boiling water resistance and weather resistance. It was good.
  • BMA n-butyl methacrylate
  • SMA trimethoxysilylpropyl methacrylate
  • GMA glycidyl methacrylate
  • amercaptopropyltrimethoxysilane 0.196 g (lnimol) in 8.49 g of toluene was added to a reaction solution of 0.025 g (0.15 ⁇ 1) of azobisisobutyronitrile. A solution dissolved in 3 g of toluene was dropped and reacted. This is called B-9.
  • n-butyl methacrylate (BMA) 5.69 g (40 mmol) 1.24 g (5 mmol) of trimethoxysilylpropyl methacrylate (SUA), 0.71 g (5 mmol) of glycidyl methacrylate (GMA), and 0.098 g (0.5 miDol) of amercaptopropyltrimethoxysilane were dissolved in 8.49 g of toluene.
  • Comparative Component B'-5 A solution obtained by dissolving 0.025 g (0.15 mmol) in 3 g of toluene was dropped and reacted. This is referred to as Comparative Component B'-5.
  • Comparative Preparation Example B'-6 The same operation as in Preparation Example Bl was performed, and n-butyl methacrylate (BMA) Og (Ommol), trimethoxysilylpropyl methacrylate (SMA) 6.20 g (25 minol), glycidyl methacrylate (GMA) 3.55 g (25 mmol), In a reaction solution obtained by dissolving 0.784 g (4 minol) of amercaptoprovir trimethoxane in 11.6 g of toluene, 0.025 g (0.15 mmol) of azobisisobutyronitrile was dissolved in 3 g of toluene. The mixture was dropped and reacted. This is referred to as Comparative Component B'-6.
  • the coating resin compositions of the examples were compared with the comparative examples in that the coating film had all of the following properties: adhesion, coating film hardness, solvent resistance, boiling water resistance and weather resistance. It was good. .
  • a pigment mixture consisting of 100 g of titanium oxide as white pigment (R-820, manufactured by Ishihara Sangyo Co., Ltd.) and lgara (manufactured by Toda Kogyo Co., Ltd.) was added to (A) component 90s. Dispersed with Glenmill. To this, the component (A) and the component (B) were further added, and the mixture was adjusted so that the weight ratio of the component (A): the component (B): the pigment was 10: 4: 10. This ratio is 18: 8: 50 in solids ratio. Further, the amounts shown in Tables 8 and 9 for the components (C) and (D) were added to obtain a coating solution.
  • the coating resin compositions of the examples were compared with the comparative examples in that the coating film had any of adhesion, coating film hardness, solvent resistance, boiling water resistance, weather resistance and gloss. Was also good. 1 2 3 4 5 6 7
  • C-1 N- -Aminoethyl -7-Ami knob mouth pillmethyldimethoxysilane
  • C-2 Dibutyltin dilaurate
  • composition of ⁇ '-5-120 Composition'-6 ⁇ compound C C-1 2 2 2 2 2
  • C-1 NS- Aminoethyl- ⁇ -Rinaminopropylmethyldimethoxysilane
  • C-2 Dibutyltin dilaurate
  • Example 1 The coating resin composition of Example 1 was coated on various substrates to prepare a resin coating, and the coating film properties were evaluated in the same manner as in Example 1. The following were used as substrates.
  • Glass plate Soda glass plate (dimensions 76 mm X 52 mm 0.7 mm).
  • Aluminum plate Surface anodized aluminum plate (Dimensions 15 Ommx 7 Omm—x 0.
  • Stainless steel plate SUS303 plate (Dimension 15 Ommx 7 Omrax 0.5 MI).
  • PC board Polycarbonate board (dimensions 10 mm X 10 mm X 2.5 mm).
  • PMMA plate Polymethyl methacrylate plate (Dimensions 1 Ommx 1 Omm 2.5 mm
  • Inorganic plate “Multi-siding” manufactured by Matsushita Electric Works, Ltd. (bulk density: 1. Og / cni 3
  • the dimension change from saturated water absorption to absolute dryness is 0.3 mm.
  • Acrylic emulsion sealer coated cement-based plate (dimension 15 Ommx 70 mm 5 mm).
  • Processed inorganic plate The above inorganic plate processed into the dimensions and shapes shown in Figs.
  • Alumina plate Alumina sintered plate for electronic circuit board manufactured by Matsushita Electric Works, Ltd. If necessary, an epoxy sealer “Epo E Sealer I” (manufactured by Isamu Paint) was used as a primer. Even if no primer is used, there is no particular problem with the adhesion, but if sufficient adhesion is required even after treatment with boiling water for 5 hours, it is preferable to use a primer.
  • Example 55-62 The resin coating of the present invention can be processed after painting as long as it is a workable substrate.
  • a stainless steel plate (SUS303) (dimensions: 15 O mm X 7 O min x 0.5 mm) is treated with a primer (Epo E-Seler (made by Isamu Paint)), and is further coated for coating in Example 1. The following processing was performed by coating the resin composition.
  • Punching Punching a hole with a diameter of 50 ⁇ with a punching press.
  • Drilling Drilling a 5mm diameter hole.
  • Cutting process Cut with a breath cutter.
  • coatings were prepared in the same manner as above, and were also subjected to primer treatment and resin coating in the same manner as described above, and the coating film performance was evaluated.
  • the primer is not limited to the above-mentioned epoxy primer, and the coating material was evaluated in the same manner as described above using the following commercially available paints and primers.
  • the specifications of the coating were in accordance with the specifications of each primer and paint, but all were applied so that the film thickness was around 1 m.
  • Epoxy Epo E Sealer (made by Isamu Paint).
  • Neo silica # 5000 made by Isaam paint.
  • Chlorinated rubber Lapearl «100 Primer (Shinto Paint).
  • Phenol type Newacnon primer (manufactured by Kansai Paint). Polyester type: Polyvest putty 100 (made by Dai Nippon Paint).
  • Example 7 1 to 75 and Comparative Example 2 1-2 3-Next, a primer containing the components (a-1) to (dl), which is particularly suitable for producing a resin coating.
  • a preparation example of the composition will be described.
  • the generated polymethylsiloxane was washed with water to remove by-product hydrogen chloride. This was heated under reduced pressure to remove water remaining as a part of the solvent, to obtain a 50% silicone resin toluene solution. Then, a solution containing the following components was prepared, and the temperature was gradually increased with stirring while removing toluene.When the temperature reached 230 ° C, heating was continued for another 5 hours while maintaining the temperature. Was.
  • the following components were mixed, and a mixture of 40 parts of methanol and 15 parts of water was added dropwise while stirring at a temperature of 25 ° C. or lower. Then, the temperature was raised to 70 ° C. with stirring, the mixture was refluxed under heating for 1 hour, and then cooled. After adding 2 parts of calcium carbonate to the collected polyorganosiloxane layer to neutralize by-product hydrogen chloride, the mixture was heated under reduced pressure to remove methanol and low-boiling compounds, thereby obtaining a liquid polyorganosiloxane. The following was added to 50 parts of the polyorganosiloxane, and the mixture was heated under xylene reflux for 3 hours. After cooling and filtration, a 50% xylene solution S-3 of an epoxy resin-modified silicone resin was obtained.
  • the coating film performance was good, and after performing the accelerated weathering test for 500 hours with a sunshine analyzer, the coating film There was no peeling, and no discoloration was observed at the t ⁇ level.
  • the preparation of the vinyl copolymer containing a hydrolyzable group is as follows.
  • the monomers shown in Table 19 are charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer. Toluene, the indicated chain transfer agent and polymerization initiator were added, and the mixture was reacted at 70 ° C. for 2 hours under a nitrogen gas atmosphere with uniform stirring.
  • the obtained vinyl copolymers having a hydrolyzable group were defined as ⁇ -1 to ⁇ -6, respectively.
  • the molecular weight was measured by the method described above.
  • the above-mentioned solutions S1 to S-3 were used as the epoxy resin-modified silicone resin.
  • a primer composition obtained by using the coating resin composition of Example 1, was prepared the same way in ⁇ co one coating material, the Table 2 t results of the evaluation in the same manner as 0 To 21.
  • Example 71 Using the primer composition used in Example 1, the following four kinds of pigments were added thereto, and the mixture was treated with a sand mill for 60 minutes and used as it was as a primer composition.
  • White White pigment (manufactured by Ishihara Sangyo) 45% added to primer solids.
  • Yellow Yellow pigment (Dainichi Seika Kogyo) 60% added to primer solids.
  • Brown brown pigment (manufactured by Dainichi Seika Kogyo) 30% added to primer solids.
  • Black black pigment (Dainichi Seika Kogyo) 25% added to primer solids.
  • the primer composition was spray applied and heat cured at 80 ° C. for 20 minutes.
  • the coating resin composition of Example 1 was applied thereon so as to have a thickness of 30 m, and was cured by heating at 80 mm for 20 minutes. The results are shown in Table 22.
  • Table 23 shows examples of imparting a high-grade appearance to the inorganic cured product by recoating.
  • the following two pigments were added to the coating resin composition of Example 1 to prepare two types of enamels.
  • Pigment 1 White pigment (Ishihara Sangyo) 61%
  • Pigment 2 White pigment (Ishihara Sangyo) ⁇ %
  • Table 24 shows an example in which a commercially available colored paint or a coloring paint according to the present invention is coated on a primer-treated base material, and further coated with a transparent paint according to the present invention.
  • the commercial intermediate coating was spray-painted according to the manufacturer's specifications. As shown in Table 24, in all cases, there was no problem in the coating film performance, and coatings with excellent durability were obtained.
  • Table 25 shows an example in which a commercially available colored paint or a colored paint according to the present invention is coated on a base material that has not been subjected to primer treatment, and further a transparent paint according to the present invention is coated. . As can be seen from Table 25, in each case, sufficient coating performance with excellent durability was obtained.
  • Epo E sealer made by Isamu Paint was used as a primer (
  • Epoxy Epo E Sealer (made by Isamu Paint)
  • Neo silica # 5000 made by Isamu Paint
  • Chloride rubber Lapearl # 100 primer (Shinto Paint)
  • Paint 100 100 100 100 Film Pencil hardness 2 H 2 H 2 H 2 ⁇
  • Monomer 4 Vinyl tris (methylethyl ketoxime) silane Monomer 5: 3-Methacryloxypropyl trimethoxy silane Monomer 6: 3-Methacryloxypropyl tris (methyl ethyl)
  • Chain transfer agent 1 3-mercaptopropyl trimethoxysilane
  • Polymerization initiator 1 azobisisobutyronitrile
  • Middle coat 1 Phthalic acid resin enamel (Univac 200, made by Nippon Paint)
  • Middle coat 2 Polyurethane resin paint (Tourethane # 100 enamel, made by Toube)
  • Middle coat 3 Acrylic paint (AP Enamel, Kansai Paint)
  • the resin composition for coating of the present invention contains the components (A), (B), and (C) or the components (A), (B), (C), and (D) as essential components, It can form a coating film with high toughness, high hardness, high weather resistance, excellent adhesion, solvent resistance, boiling water resistance, and high-speed drying property. Since this coating film has excellent toughness, it does not crack at film thicknesses up to 50 zm, has little uneven coating, and has a wide adaptability to substrate irregularities. It can also widely respond to dimensional changes due to temperature and humidity of the substrate.
  • the resin composition for coating of the present invention can be cured both at room temperature and under heat, and can be used in a wide range of drying and curing conditions or temperature. Therefore, it can be applied to base materials with poor heat resistance, and can be applied to work sites where heat is not applied, so its industrial value is high. Further, the coating resin of the present invention has high stability during storage, and can be stored for a long time even when a pigment is dispersed and blended, and can be arbitrarily colored.
  • the resin composition for coating having the above excellent performance can be easily obtained.
  • the resin-coated product according to the present invention has a cured resin layer of the resin composition for coating on the surface of the base material, it has high toughness, high hardness, high weather resistance, adhesion, solvent resistance, and boiling resistance. It has a coating that is excellent in water-based and high-speed drying properties. Since this coating film has excellent toughness, it does not crack at a film thickness of up to 50 ⁇ m, has less coating unevenness, and has a wide adaptability to unevenness of the substrate. In addition, it can widely respond to dimensional changes due to the temperature and humidity of the substrate.
  • the resin coating according to the present invention can be produced using the above-mentioned resin composition for coating which can be cured both at room temperature and under heat, it can be produced in a wide range of dry curing conditions or temperatures. Therefore, a substrate having poor heat resistance can be used, and it can be manufactured even in a work site where heat is not applied, so that its industrial value is high. Furthermore, the resin coating of the present invention has high stability during storage, can be stored for a long time even when a pigment is dispersed and blended, and can be produced using a coating resin composition that can be arbitrarily colored. High designability and wide range of use. According to the method for producing a resin coating according to the present invention, the above excellent resin coating can be easily obtained.

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Abstract

Composition de résine de revêtement permettant d'obtenir un film de revêtement de qualité remarquable non seulement quant à la dureté et à la résistance aux intempéries mais aussi quant à la robustesse à l'aptitude à la prise à froid comme à chaud et quant à l'obtention d'un film de revêtement d'excellente stabilité ou stockage. Cette composition renferme, comme composants essentiels, une solution d'un oligomère organosilane renfermant des silices en dispersion, élaborées par hydrolyse partielle d'un organosilane hydrolysable de la formule générale: R1nSiX4-n dans des silices colloïdales en dispersion dans un solvant organique, de l'eau ou un mélange de sa substance, une résine acrylique constituant un copolymère renfermant des esters d'acrylate et/ou des esters de méthacrylate de la formule générale: CH2=CR2(COOR3), et un catalyseur de durcissement. Cette composition consiste en un système liquide à deux parties et les composants en sont mélangés de manière appropriée avant utilisation. Elle est appliquée sur la surface d'un substrat pour constituer une couche renfermant un produit de durcissement.
PCT/JP1996/001036 1995-04-21 1996-04-16 Composition de resine de revetement WO1996033243A1 (fr)

Priority Applications (4)

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KR1019970707487A KR100250342B1 (ko) 1995-04-21 1996-04-16 코팅용 수지 조성물
US08/750,745 US6090873A (en) 1995-04-21 1996-04-16 Coating resin composition containing a hydrolyzable organosilane and an acrylic resin
EP96909379A EP0822240B1 (fr) 1995-04-21 1996-04-16 Composition de resine de revetement
DE69623947T DE69623947T2 (de) 1995-04-21 1996-04-16 Beschichtungsharzmasse

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JP7/97291 1995-04-21
JP9729195 1995-04-21

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US09/572,287 Division US6329456B1 (en) 1995-04-21 2000-05-17 Coating resin composition containing hydrolyzable organosilane, acrylic resin and polyorganosiloxane

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EP0851009A3 (fr) * 1996-12-24 1998-09-02 Matsushita Electric Works, Ltd. Composition de revêtemnt antiadhésive et anti-fouling et articles revêtus
US7582351B2 (en) 2001-10-25 2009-09-01 Panasonic Electric Works Co., Ltd. Composite thin film holding substrate, transparent conductive film holding substrate, and panel light emitting body

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EP0955275B1 (fr) * 1998-04-27 2002-06-26 Toyo Ink Manufacturing Co., Ltd. Composition de revêtement pour la coloration de verre, méthode de sa production et son utilisation
US7790292B2 (en) 1999-05-18 2010-09-07 Sabic Innovative Plastics Ip B.V. Polysiloxane copolymers, thermoplastic composition, and articles formed therefrom
CN1280367C (zh) 2000-01-12 2006-10-18 国际涂料有限公司 室温固化的涂料组合物
US8022058B2 (en) * 2000-05-10 2011-09-20 The Trustees Of Columbia University In The City Of New York Agents for preventing and treating disorders involving modulation of the RyR receptors
US7879840B2 (en) 2005-08-25 2011-02-01 The Trustees Of Columbia University In The City Of New York Agents for preventing and treating disorders involving modulation of the RyR receptors
DE10022992A1 (de) * 2000-05-11 2001-12-06 Wacker Polymer Systems Gmbh Funktionalisierte Copolymerisate für die Herstellung von Beschichtungsmitteln
KR100387734B1 (ko) * 2000-06-17 2003-06-18 삼성종합화학주식회사 올레핀 중합용 촉매 및 중합방법
US7445848B2 (en) 2000-06-23 2008-11-04 Akzo Nobel Coatings Internationals B.V. Ambient temperature curing coating composition
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KR20020020599A (ko) * 2000-09-09 2002-03-15 황성호 자외선경화형 실리콘코팅제 조성물
US20050109238A1 (en) * 2001-10-25 2005-05-26 Takeyuki Yamaki Coating material composition and article having coating film formed therewith
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DE69623947T2 (de) 2003-06-05
US6090873A (en) 2000-07-18
CN1071367C (zh) 2001-09-19
CN1181775A (zh) 1998-05-13
EP0822240B1 (fr) 2002-09-25
EP0822240A4 (fr) 1998-09-09
US6329456B1 (en) 2001-12-11
KR19990007963A (ko) 1999-01-25
EP0822240A1 (fr) 1998-02-04
DE69623947D1 (de) 2002-10-31

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